Water Softening

Methods

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 Water Softening Methods
❖ Zeolite (Permutit process)

❖ Ion-exchange

❖ Mixed bed ion-exchange

❖ Reverse Osmosis

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 Permutit or Zeolite Process
o Zeolite is hydrated sodium aluminium silicate having a general formula,
Na2OAl2O3.xSiO2.yH2O.
o It exchanges Na+ ions for Ca2+ and Mg2+ ions.
o Common Zeolite is Na2OAl2O3.3SiO2.2H2O known as natrolith.
o Other gluconites, green sand (iron potassium phyllosilicate with characteristic
green colour, a mineral containing Glauconite)etc. are used for water softening.
o Artificial zeolite used for water softening is Permutit.
o These are porous, glassy particles having higher softening capacity compared to
green sand.
o They are prepared by heating china clay (hydrated aluminium silicate), feldspar
(KAlSi3O8-NaAlSi3O8 – CaAl2Si2O8) are a group of rock-forming tectosilicate
minerals which make up as much as 60% of the earth’s crust) and soda ash
(Na2CO3)
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Natural Zeolites:

1. Natrolite - Na2O. Al2O3 4SiO2 .2H 2O

2. Laumontite - CaO. Al2O3 4SiO2 .4H 2O

3. Harmotome - (BaO.K2O). Al2O3 5SiO2 .5H 2O

- Capable of exchanging its Na ions

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 Permutit or Zeolite Process

o Method of softening:

Na2Ze + Ca(HCO3)2 2 NaHCO3+CaZe

Na2Ze + Mg(HCO3)2 2 NaHCO3+ MgZe
Na2Ze + CaSO4 2 Na2SO4+CaZe
Na2Ze + CaCl2 2 NaCl+CaZe

o Regeneration of Zeolite:

CaZe (or) MgZe + 2 NaCl Na2Ze + CaCl2 or MgCl2

Brine solution

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 Zeolite Process
o Advantages:
o Residual hardness of water is about 10 ppm only
o Equipment is small and easy to handle
o Time required for softening of water is small
o No sludge formation and the process is clean
o Zeolite can be regenerated easily using brine solution
o Any type of hardness can be removed without any
modifications to the process

o Disadvantages:
o Coloured water or water containing suspended impurities
cannot be used without filtration
o Water containing acidic pH cannot be used for softening since
acid will destroy zeolite.
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 Ion-Exchange Process
o Ion-exchange resins are cross linked long chain polymers with
microporous structure
o Functional groups present are responsible for ion-exchange
properties
o Acidic functional groups (-COOH, -SO3H etc.) exchange H+ for
cations &
o Basic functional groups (-NH2, =NH etc.) exchange OH- for
anions.
A. Cation-exchange Resins(RH+):
- Styrene divinyl benzene copolymers
- When sulphonated, capable of exchange H+

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 Ion-Exchange Process
B. Anion-exchange resins (R’OH):
- Styrene divinyl benzene copolymers or amine formaldehyde copolymers with
NH2, QN+, QP+, QS+, groups.
- On alkali treatment, capable of exchange of OH-

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 Ion-Exchange Process
The Process of Ion-exchange is:

2 RH+ + Ca2+/Mg2+ R2Ca2+/R2Mg2+ + 2 H+ (Cation exchange)

R’OH- + Cl- R’+ Cl- + OH- (anion exchange)

2 R’OH- + SO42- R’2 SO42- + 2 OH- (anion exchange)

2 R’OH- + CO32- R’2 CO32- + 2 OH- (anion exchange)

Finally,
H+ + OH- H2 O
Regeneration of exhausted resins:
Saturated resins are regenerated:
R2Ca2+/R2Mg2+ + 2H+ 2 RH+ + Ca2+/Mg2+ (cation) (Strong acid)
(washings)
R’2 SO42- + 2 OH- 2 R’OH- + SO42- (Strong base)
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 Ion-Exchange Process

Note: Hard water should be first passed through the cation exchanger and then
Anion exchanger to avoid hydroxides of Ca2+ and Mg2+ getting formed
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 Mixed Bed Deionizer

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 Advantages & Disadvantages of
ion-exchange process
o Advantages:
- Can be used for highly acid and highly alkaline water
- Residual hardness of water is as low as 2 ppm.
- Very good for treating water for high pressure boilers

o Disadvantages:
- Expensive equipment and chemicals
- Turbidity of water should be < 10 ppm. Otherwise output will
reduce; turbidity needs to be coagulated before treatment.
- Needs skilled labour

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 Reverse Osmosis
oWhen two solutions of unequal
concentrations are separated by a
Semipermeable membrane,
solvent will flow from lower
conc. to higher conc.

oThis phenomenon can be reversed

(solvent flow reversed) by
applying hydrostatic pressure on
the concentrated side

oIn reverse osmosis, pressure of

15-40 kg/cm2 is applied to sea
water.

oThe water gets forced through the

semipermeable membrane leaving
behind the dissolved solids.
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12/12/2021 20
 Module VI
FUELS & COMBUSTION
INTRODUCTION AND SOLID FUELS
 Introduction

• Most chemical fuels are found in nature in the form of

crude oil, natural gas, and coal.

• These fuels are called fossil fuels because they have

been formed by the decay of vegetable and animal
matter over millions of years under conditions of high
pressure and temperature and absence of oxygen.

.
 FUELS
Fuel is a combustible substance which when burnt in
oxygen or air, produces significant amount of heat which
can be economically used for domestic and industrial
purposes for generating power.
In the process of combustion, the chemical energy of
fuel is converted into heat energy.
• Fuel + Air/oxidizer  Products of combustion + Energy
 Classification of Fuels

Based on origin

Natural / Primary Fuels Synthetic / Derived Fuels

Based on physical state Based on physical state

Liquid
Liquid Solid Fuels Gaseous
Solid Fuels Gaseous Fuels Fuels
Fuels Fuels Examples
Examples Examples
Examples Examples Oils from
Examples Charcoal Producer gas
Petroleum Natural petroleum
Wood Coke Water gas
or Gas distillation
Coal Briquettes Coal gas
Crude oil Coal tar,
Oil shale
Shale-oil
Alcohols
 CHARACTERISTICS OF GOOD FUEL
1. HIGH CALORIFIC VALUE:
A good fuel should have high calorific value i.e. it
should produce large amount of heat on burning.

CALORIFIC VALUE

• The quantity of heat liberated by the complete

combustion of unit weight (1gm or 1kg) of the fuel in
air or oxygen.
Calorific Values of Important Fuels

FUELS CALORIFIC VALUES

(kilo joules per kg)
Cow dung cake 6000 - 8000
Wood 17000 - 22000
Coal 25000 - 33000
Petrol 45000
Kerosene 45000
Methane 50000
CNG 50000
LPG 55000
Biogas 35000 - 40000
Hydrogen 150000
2. MODERATE IGNITION TEMPERATURE

Ignition temperature: Lowest temperature to

which fuel must be preheated so that it starts burning
smoothly. If ignition temperature is low, the fuel catches
fire easily.
Low ignition temperature is dangerous for storage and
transportation of fuel. High temperature causes difficulty
in ignite. So, a good fuel should have moderate ignition
temperature.
IGNITION TEMPERATURES OF SELECTED FUELS

Substance Ignition Temp

Hydrogen 1085⁰F

Carbon 925⁰F

Sulphur 450⁰F

Coal 750⁰F

Wood 450⁰F

Kerosene 490⁰F
3. LOW MOISTURE CONTENT
A good fuel should have low moisture content as moisture
content reduces the calorific value.

4. LOW NON-COMBUSTIBLE MATTER CONTENT

A good fuel should have low contents of non-combustible
material as non-combustible matter is left in form of ash
which decreases the calorific value of fuel
5. MODERATE RATE OF COMBUSTION
The temperature of combustion of fuel depends upon the
rate of combustion . If the rate of combustion is low, then
required high temperature may not be reached soon. On
the other hand ,too high combustion rate causes high
temperature very quickly.
6. MINIMUM SMOKE AND NON-POISONOUS GASES
On burning, fuel should not give out objectionable and
poisonous gases. In other words, gaseous products should
not pollute the atmosphere. Examples:
CO- Poisonous or toxic gas
SO2, SO3, NOx - responsible for acid rain
CO2 - results in global warming
7.CHEAP
A good fuel should be cheap and readily available.
8. EASY TRANSPORTATION
A good fuel should be easy to handle and transport at low
cost
 Calorific value of fuels

• The most important property of fuel to be taken into

account is its calorific value or the capacity to supply
heat. The calorific value of a fuel can be defined as
"the total quantity of heat liberated when a unit mass or
volume of the fuel is burnt completely".
• Units are Calorie/ Kilocalorie - Calorie is the amount
of heat required to raise the temperature of one gram
of water through one degree centigrade.
Determination of Calorific Value

Bomb calorimeter
Higher or Gross Calorific Value (HCV or GCV)
• Usually, all fuels contain some hydrogen and when the
calorific value of hydrogen containing fuel is determined
experimentally, the hydrogen is converted to steam.
• If the products of combustion are condensed to room
temperature (15C or 60F), the latent heat of condensation
of steam also gets included in the measured heat, which is
then called "higher or gross calorific value".
• So gross or higher calorific value may be defined as "the total
amount of heat produced when one unit mass/volume of the
fuel has been burnt completely and the products of
combustion have been cooled to room temperature".
 Lower or Net Calorific Value

• In actual use of fuel, the water vapour and moisture etc are not
condensed and escapes as such along with hot combustion gases.
Hence a lesser amount of heat is available. So, net or lower calorific
value may be defined as "the net heat produced when unit mass /
volume of the fuel is burnt completely and the products are
permitted to escape".
• Net or lower calorific value can be found from GCV value
NCV = GCV - Latent heat of water vapour formed
= GCV - Mass of hydrogen x 9 x latent heat of steam
• 1 part by mass of hydrogen produces 9 parts by mass of water. The
latent heat of steam is 587 k cal / kg or 1060 B. Th. U. / lb of water
vapour formed at room temperature. (ie 15C).
 Calculation

m = mass of fuel pellet (g)

W = mass of water in the calorimeter (g)
w = water equivalent of calorimeter (g)
t1 = initial temperature of calorimeter.
t2 = final temperature of calorimeter.
HCV = gross calorific value of fuel.
 Water Equivalent of the calorimeter is determined by
burning a fuel of known calorific value (benzoic acid (HCV
= 6,325 kcal/kg) and naphthalene (HCV = 9,688 kcal/kg)

If H is the percentage of hydrogen in fuel,

the mass of water produced from 1 g of fuel = (9/100)×H
= 0.09 H

Heat taken by water in forming steam = 0.09 H× 587 cal

(latent heat of steam = 587 cal/kg)

LCV = HCV – Latent heat of water formed

16
1. 0.72 gram of a fuel containing 80% carbon, when burnt
in a bomb calorimeter, increased the temperature of water
from 27.3o to 29.1oC. If the calorimeter contains 250
grams of water and its water equivalents is 150 grams,
calculate the HCV of the fuel. Give your answer in KJ/Kg.

Solution. Here x= 0.72 g, W = 250g, t1 = 27.3oC, t2 = 29.1oC.

HCV of fuel (L) = (W + w) (t1 - t2) Kcal/kg

x
= (250 + 150) × (29.1-27.3) kcal/kg = 1,000 × 4.2 kJ/Kg = 4,200 kJ/kg
0.72

17
2. On burning 0.83 of a solid fuel in a bomb calorimeter , the
temperature of 3,500g of water increased from 26.5oC to 29.2oC.
Water equivalent of calorimeter and latent heat of steam are
385.0g of and 587.0 cal/g respectively. If the fuel contains 0.7%
hydrogen, calculate its gross and net calorific value.

Solution. Here wt. of fuel (x) = 0.83 g of ; wt of water (W) = 3,500

g; water equivalent of calorimeter (w) = 385 g ; (t2 - t) = (29.2oC -
26.5oC) = 2.7oC ; percentage of hydrogen (H) = 0.7% ; latent heat
of steam = 587 cal/g
Gross calorific value = (W + w) (t1 - t2) cal/g
x
= (3,500 +385) × 2.7 = 12,638 cal/g
0.83
NCV = [GCV – 0.09 H × 587]
= (12,63 8– 0.09 × 0.7 × 587) cal/g
= (12,638 – 37) cal/g = 12,601 cal/g
18
1. Fuse wire correction
2. Acid correction
3. Cooling correction
19
 Corrections

Fuse wire correction:

Heat liberated during sparking should be subtracted
from calorific value

20
Acid correction:
Fuels containing Sulphur and Nitrogen if oxidized, the heats of formation of
H2SO4 and HNO3 should be subtracted (as the acid formations are
exothermic reactions)

21
22
Cooling correction:
The rate of cooling of the calorimeter from maximum temperature to room
temperature is noted. From this rate of cooling (i.e., dt°/min) and the actual time
taken for cooling (X min) then correction (dt × X) is called cooling correction
and is added to the (t2 . t1) term.

23
 (W+w) (t2-t1+Cooling Correction) – (Acid + Fuse Correction)
GCV =

Mass of the fuel (x)

24
3. A sample of coal contains C =93%; H =6% and ash = 1%. The following data
were obtained when the above coal was tested in bomb calorimeter.
Wt. of coal burnt =0.92g
Wt. of water taken =550g
Water equivalent of calorimeter =2,200g
Rise in temperature =2.42 oC
Fuse wire correction =10.0 cal
Acid correction =50.0 cal
Calculate gross and net calorific value of the coal, assuming the latent heat of
condensation of steam as 580 cal/g.
Solution: Wt. of coal sample (x) = 0.92 g; wt. of water (W) =550 g;
water equivalent of calorimeter (w) = 2,200g;
temperature rise (t2-t1) = 2.42 oC;
acid correction = 50.0cal;
fuse wire correction = 10.0 cal;
latent heat of steam = 580 cal/g;
percentage of H =6%
25
GCV = (W + w) (t1 - t2) –[acid+fuse corrections]
x
= (550+2,200) × 2.42 – [50+10] cal
0.92g
= 7,168.5 cal/g.

NCV = [GCV – 0.09 H × latent heat steam]

= (7168.5 – 0.09 × 6 × 580) cal/g
= 6855.3 cal/g

26
 Boy’s Calorimeter
It is used for measuring the calorific value of gaseous (or)
liquid fuels.
Principle
•A known volume of gaseous fuel sample is burnt in the
combustion chamber of a Boy’s calorimeter.
•The released heat is quantitatively absorbed by cooling
water, circulated through copper coils surrounding the
combustion chamber.
•The mass of cooling water and its rise in temperature
are noted.
•The mass of water produced by condensation of steam
is calculated.
•The calorific value of the fuel sample is then calculated
from these data.
27
Construction
Boy‘s calorimeter consists of a combustion chamber
surrounded by water tube with two thermometers T1 and
T2 attached. There is a burner in the chamber, which is
connected to a gas tube.
Working
 A known volume of water is passed through the tubes.
 The initial temperature is noted when the two
thermometers show the same constant temperature.
 A known volume of the gas (measured using a meter) is
passed through the tube and burnt in the combustion
chamber.
 The heat liberated is absorbed by the water in the tubes.
 The final temperature of water is noted.
 The gaseous products are cooled and condensed into a
measuring jar.
28
29
Calculation
 Knocking
• In an internal combustion engine, a mixture of gasoline vapour and air
is used as a fuel.

• After the initiation of the combustion reaction by spark in the

cylinder, the flame should spread rapidly and smoothly through the
gaseous mixture, thereby the expanding gas drives the piston down
the cylinder.

• The ratio of the gaseous volume in the cylinder at the end of the
suction-stroke to the volume at the end of compression-stroke of the
piston is known as the 'compression ratio'.

• The efficiency of an internal combustion engine increases with the

compression ratio.
• Compression ratio (CR) is defined as the ratio of the cylinder volume
(V1) at the end of the suction stroke to the volume (V2) at the end of
the compression stroke of the piston.

• V1 being greater than V2, the CR is >1.

• The CR indicates the extent of compression of the fuel-air-mixture by

the piston.

• However, successful high compression ratio is dependent on the

nature of the constituents present in the gasoline used.

• In certain circumstances, due to the presence of some constituents in

the gasoline used, the rate of oxidation becomes so great that the last
portion of the fuel-air mixture gets ignited instantaneously producing
an explosive violence, known as 'knocking'.

• The knocking results in loss of efficiency, since this ultimately

decreases the compression ratio.
 Chemical structure and knocking
• The tendency of fuel constituents to knock is in the
following order. Straight - chain paraffins > branched - chain
paraffins (isoparaffin) > olefins > cyclo paraffins (naphthenes)
> aromatics.

Octane number
• The most common way of expressing the knocking
characteristics of a combustion engine fuel is by 'octane
number', introduced by Edger. It has been found that n-
heptance, knocks very badly and hence, its anti-knock value
has arbitrarily been given zero.
 Octane number
• Octane number is equal to the percentage by volume of iso-octane
(2,2,4-trimethyl pentane) in a mixture of n-heptane and iso-octane
having the same knocking tendency compared to the sample of gasoline
being tested;
• Iso-octane has the best antiknocking properties and assigned an octane
number of 100 whereas n-heptane has poor antiknocking property and
assigned an octane number of zero.
• The hydrocarbons present influence the knocking properties of gasoline
which vary according to the series:
straight chain paraffin > branched chain paraffin > olefin >
cycloparaffin > aromatics.
• The fuel which has same knocking tendency with the mixture having
80% iso-octance has octane number 80.
 H H H H H H H

H C C C C C C C H

H H H H H H H

n-heptane

CH 3

CH 3 C CH 2 CH CH 3

CH 3 CH 3

Isooctane
 Improvement of anti-knock characteristics of a fuel
• The octane number of many otherwise poor fuels can be raised
by the addition of tetra ethyl lead (C2H5)4Pb or TEL and diethyl
telluride (C2H5)2Te. In motor spirit (Motor fuel) about 0.5ml
and in aviation fuel 1.0 - 1.5ml of TEL is added per litre of
petrol.

• TEL is converted into a cloud of finely divided lead and lead

oxide particles in the cylinder and these particles react with any
hydrocarbon peroxide molecules formed, thereby slowing down
the chain oxidation reaction and thus decreasing the chances of
any early detonation.

• However deposit of lead oxide is harmful to the engine life. In

order to help the simultaneous elimination of lead oxide formed
from the engine, a small amount of ethylene dibromide (or
ethylene dichloride) is also added to petrol.

• The added ethylene dibromide removes lead oxide as volatile

lead bromide along with the exhaust gases. The presence of
sulphur compounds in petrol reduces the effectiveness of the
TEL. TEL is more effective on saturated hydrocarbons than on
unsaturated ones.
 Other additives

• Oxidation inhibitors - 2,4 - ditertiary butyl - 4 - methyl phenol.

• Rust inhibitors - Organic compounds of phosphorus or

antimony.

• Ignition control additives - tricresyl phosphate which

suppresses pre-ignition of the fuel due to glowing deposits on
spark plug or a hot spot on the cylinder wall.
 Diesel Engine Fuels

Characteristics of an ideal diesel oil

• It should have low spontaneous ignition

temperature.
• It should have very little sulphur, aromatic and
ash content.
• The ignition lag should be as short as possible.
 Knocking in Diesel Engines
• In a diesel engine, the fuel is exploded not by a spark, but by the
application of heat and pressure. In the cycle of operations of a
diesel engine, air is first drawn into the cylinder and compressed.
• Towards the end of the compression stroke, the fuel (diesel oil) is
injected as a finely-divided spray into air in the cylinder heated to
about 500C by compression.
• The oil absorbs the heat from the air and if it attains its ignition
temperature the oil ignites spontaneously. The pressure of the
gases is further increased by the heat accompanying the ignition of
the oil.
• The piston is pushed by the expanding gases and this constitutes
the power stroke.
• Fuel feed and ignition continue during this down stroke. The fuel
injection stops at the exhaust stroke.
• Diesel engine fuels consist of longer chain hydrocarbons than internal
combustion engine fuels.

• The main characteristic of diesel engine fuel is that it should easily ignite below
compression temperature.

• There should be as short an induction lag as possible. This means that it is

essential that the hydrocarbon molecules in a diesel fuel should be as far as
possible the straight-chain ones with a minimum admixture of aromatic and
side-chain hydrocarbon molecules.

• The suitability of a diesel fuel is determined by its cetane value, which is the
percentage of hexadecane in a mixture of hexadecane and 2-methyl
naphthalene, which has the same ignition characteristics as the diesel fuel
sample, under the same set of conditions.

• The cetane number of a diesel fuel can be raised by the addition of small
quantity of certain "pre-ignition dopes" like alkyl nitrites such as ethyl nitrite,
iso-amyl nitrite, acetone peroxide.
 H H H

H C C C H
14
H H H
n-Hexadecane (Cetane No. = 100)

CH3

2-Methyl naphthalene (Cetane No. = 0)

 Ignition quality decreases among
hydrocarbons is as follows

• n-alkanes > naphthalenes > alkenes > branches

alkanes > aromatics

• Cetane number decreases

• Ignition quality decreases
• Ignition delay increases
 Module 7C
CORROSION CONTROL
 Spontaneity of Corrosion
Metal has natural tendency to go to Thermodynamically stable
state
Metals (thermodynamically unstable) are usually extracted from
ores (thermodynamically stable) through the application of a
considerable amount of energy
Corrosion (oxidation)
Metal Ore (metallic compd) Energy
(T.D.Unstable) T.D.Stable
Metallurgy (reduction)
The energy required to convert ore to metallic state is returned
when the metal corrodes to form the original compound.
The tendency of metal to release this energy by corrosion, is
reflected by the relative positions of pure metals in the
electrochemical series.
 Rust formation in iron

4Fe + 3O2 + 6H2O → 4Fe(OH)3

Protective coatings
oProtective coating provide a physical barrier between
the metal and the environment.
oThey not only give corrosion protection but also add to
the decorative value of the article.

oCoatings are broadly divided as:

a) Inorganic coatings : metallic and chemical conversion

coatings
b) Organic coatings : paints, varnishes, enamels,
lacquers

4
Protective coatings
Metallic coatings:
a) Anodic coatings
b) Cathodic coatings

a) Anodic coatings:
o Anodic coatings are given on cathodic metals using metals which are more
anodic.
o Zinc, aluminium, cadmium coatings on iron are anodic coatings.
o If the coating breaks, then a galvanic couple is set up and corrosion rate gets
enhanced.
o During this process, the anodic coating gets disintegrated but it protects the
cathodic base metal.
o Hence, the anodic metal sacrifices itself to protect the base metal.
o This type of coating is known as galvanisation.
5
Protective coatings
Cathodic coatings:

o Cathodic coatings are given on anodic metals using metals which are more cathodic.

o Coating of tin, chromium, nickel on iron surface are cathodic coatings.

o If there is a discontinuity in the coating, then galvanic couple will form with base
metal as anode and the coated metal as cathode.

o Then the process of corrosion will start by the base metal ions going into solution
and the metal deteriorating.

o To avoid this, the article is checked and re-plated periodically so that there is no
discontinuity in the coating.

6
Protective coatings
Methods of metallic coatings:

a) Hot dipping
b) Metal cladding
c) Electroplating
d) Electrolessplating
e) PVD
f) CVD

a) Hot dipping:

Two types of hot dipping techniques are known:

i) Galvanizing: Dipping the base metal iron in molten zinc metal solution

ii) Tinning : Dipping the base metal iron in molten tin metal solution.
7
 Electroplating
o It is a process by which a coating metal is deposited on the base metal by passing
direct current through an electrolytic solution, containing the soluble salt of the
coating metal.

o Electroplating is done for improving

a) corrosion resistance
b) wear resistance
c) chemical resistance
d) surface hardness
e) appearance

o Both ferrous and non-ferrous metals are plated with Ni, Cr, Cu, Zn, Pb, Al, Ag, Au, Sn
etc.
o Electroplating is mainly used in automobile, aircraft, refrigerator, chemical and
electrical appliances etc.
 Electroplating

Plating bath solution

o It is a highly conducting salt solution of the metal which is to be plated.
o The level of the plating bath should cover completely the cathode and sufficient
area of anode.
o It should be good conductor and highly soluble.
o It should not undergo hydrolysis, oxidation, reduction and other chemical changes. 9
 Electroplating with Nickel on Copper

Copper Cathode is reduced Nickel Anode is oxidized

(accepts electrons) (gives electrons)

Ni2+ ions within solution become attracted

to Copper cathode
Important Factors of electroplating
o Cleaning of the article is essential for strong adherence of the electroplating:
- Scraping, grinding, sand blasting, wire brushing, solvent cleaning and acid pickling
are used for surface cleaning.
- A well cleaned and properly pre treated surface of any material to be electroplated
is necessary for obtaining the coating of long life.
o Concentration of the electrolyte is another important factor:
- Low concentration of metal ions will give uniform coherent deposition.
- To maintain low conc. of metal ions, complexing agents are added to the electrolyte.
o Thickness of the deposition should be optimised to get a strong and adherent
deposition:
- For corrosion protection multiple coatings are given to get impervious coating
without any discontinuity.
- For decorative purpose, thin coating is given.
o Current density
- Current density is the current per unit area of the article being plated (amps cm-2).
- The C.D should be maintained at optimal level to get uniform and adherent
deposition. 11
 Important Factors of electroplating
o Additives to electrolytic bath
- Additives to electrolyte are added in small quantities to get strong adherent
deposition.

- Commonly used additives are gelatin, glue, glycine, boric acid etc. and
brighteners for bright plating.

o pH of the bath:
- For a good electrodeposit, the pH of the bath must be properly maintained.
For most plating baths, pH ranges from 4 to 8.

o Method of Electroplating:
- Method depends upon the type of metal to be electroplated, the size and
type of article to be electroplated.
- Its main objectives and economics are also considered.

12
 Electroless plating
Electroless plating, also known as chemical or auto-catalytic plating, is a non-
galvanic plating method that involves several simultaneous reactions in an aqueous
solution, which occur without the use of external electrical power.
The process is a chemical reaction and is autocatalytic.
It is mainly different from electroplating by not using external electrical power.
The deposition rate is normally 12.5 – 25 um (0.0005 – 0.001 in).
The plating thickness tends to be uniform compared to electroplating due to the
absence of electric fields and the associated problems in making them uniform.
Typically nickel and copper are used in electroless platings.
In the case of nickel, the deposits are dense, relatively hard and brittle.
Electroless Nickel is not as bright as electroplated, easy to solder and braze, but
difficult to weld.
Autocatalytic platings are widely used for machine frames, base plates, fixtures,
some machine parts where metal-to-metal wear applications are needed and the
conventional oils and greases can not be used.
 Theory of Autocatalytic Platings
Electroless plating is the process of deposition of
metal on a catalytical active surface by using suitable
reducing agent without using electric current.

For example;
The electroless plating involving a nickel sulfate bath
has the following reaction:

NiSO4 + NaH2PO2 + H2O Ni + NaH2PO3 + H2SO4

Copper electroless deposition is done by reduction of alkaline
solution containing copper (II) ion Stabilized by EDTA. Here
formaldehyde acts as reducing agent.
Electroless Plating Electroplating
• CONTROL OF CORROSION BY MODIFYING
THE SURFACE
• Modifying the surface by application of
protective coatings.
• The coated surface isolates the underlying
metal from the corroding environment.
• The coating applied must be chemically
inert to the environment under particular
condition of temp. and press.
• Protective coatings are
• Metallic coatings, Non-metallic coatings
and Organic coatings
 Physical Vapour Deposition
o This is a process of depositing some material by atom by atom or
molecule by molecule or ion by ion.

Applications:
1. This process is widely used to produce decorative coatings on plastic parts
those are resembling shiny metal.

2. Many automobile parts are plastic with a PVD coating of aluminium.

3. A lacquer coating is applied over the decorative coating to provide corrosion

protection.

4. This process is also used to apply relatively thick (1mm) coatings of heat
resistant materials on jet engine parts, A special alloy of chromium, aluminium
and yttrium is used for this type of coating.

18
 PVD: – 1. Thermal Evaporation Method

Al and Au are quite usable in thermal evaporation system with heated

crucible, for they can be melt in crucible and generate enough quantity of
vapours.
However, W and Ti are not suitable for their low vapour pressure.
Typical deposition rates in industry is around 0.5 µm/min (~8 nm/s, for Al)19
 PVD: 2 – Sputtering Method
Sputtering :
A popular method for adhering thin films onto a substrate.
Sputtering is done by bombarding a target material with a charged gas (typically
argon) which releases atoms in the target that coats the nearby substrate.
It all takes place inside a magnetron vacuum chamber under low pressure.
1. High technology coatings such as ceramics, metal alloys and organic and inorganic
compounds are applied by sputtering.
2. The substance to be coated is connected to a high voltage DC power supply.
3. When the vacuum chamber has been pumped down, a controlled amount of argon or
another gas is introduced to establish a pressure of about 10-2 to 10-3 torr.
4. On energizing current supply, plasma is established between the work and the material to
be coated.
5. The sputtering gas is often an inert gas such as argon. For efficient momentum transfer, the
atomic weight of the sputtering gas should be close to the atomic weight of the target, so
for sputtering light elements neon is preferable, while for heavy elements krypton or
xenon are used. Reactive gases can also be used to sputter compounds.

20
 PVD: 2 – Sputtering Method
Sputtering is a process whereby particles are ejected from a solid target material
due to bombardment of the target by energetic particles.

Sputtering is done either using DC voltage (DC sputtering) for metals or using AC
voltage (RF sputtering) for dielectric materials and polymers.
The gas atoms are ionized and they
bombard the material to be coated.

The energy of imposing ions cause

atoms of the target material to be
sputtered off and they are transported
through the plasma to form a coating.

Direct current sputtering is used when

the target is electrically conductive.

Radio-frequency sputtering, which uses

a RF power supply is used when the
target is a non conductor such as
polymer.
21
Figure : PVD by sputtering process
 PVD: 2 – Sputtering Method
Plasma is a “state of matter similar to gas in which a certain portion of the particles
are ionized”
• The main principle is to build a vaccum chamber and fill with Argon

• By adding a high voltage, the argon will arc to plasma state

• The argon ion (Ar+) will move toward to cathode with high speed and sputter the
target material (use target as cathode).

• The target atom or molecular will be hit to substrate surface and condense as a
film.

• Instead of heat melting in evaporation method, the plasma Ar+ ion hit and sputter
the target is the main mechanism in plasma sputtering method.

• The target atom is knocked out by Ar+ ion, the knock force is so big and can
accelerate target atom a high speed. With such velocity, the target atom can hit
and attach to substrate surface deeply.

• The film density is good compared to thermal evaporation.

 PVD: 2 – Sputtering Method
Applications of Sputtering method:

o This method is used in VLSI fabrication

(Very-large-scale
integration (VLSI) is the process of creating an integrated circuit (IC) by
combining hundreds of thousands of transistors or devices into a single chip)

o Sputtering is used extensively in the semiconductor industry to deposit thin films of

various materials in integrated circuit processing.
o Thin antireflection coatings (MgF2 and Fluoropolymers; mesoporous silica materials;
titanium nitride and niobium nitride) on glass for optical applications are also
deposited by sputtering.
o An important advantage of sputter deposition is that even materials with very high
melting points are easily sputtered while evaporation of these materials in a resistance
evaporator or Knudsen cell is problematic or impossible. Sputter deposited films have
a composition close to that of the source material.

23
Sputtering offers the following advantages over other PVD methods used in
VLSI fabrication:
1) Sputtering can be achieved from large-size targets, simplifying the deposition
of thins with unifrom thickness over large wafers;
2) Film thickness is easily controlled by fixing the operating parameters and
simply adjusting the deposition time;
3) Control of the alloy composition, as well as other film properties such as
step coverage and grain structure, is more easily accomplished than by
deposition through evaporation;
4) Sputter-cleaning of the substrate in vacuum prior to film deposition can be
done;

Sputtering, however, has the following disadvantages too:

1) High capital expenses are required;

2) The rates of deposition of some materials (such as SiO2) are relatively low;
3) Some materials such as organic solids are easily degraded by ionic
bombardment;
4) Sputtering has a greater tendency to introduce impurities in the substrate
than deposition by evaporation because the former operates under a lesser
vacuum range than the latter.
Computational chemistry is the use of computers to
solve the equations of a theory or model for the
properties of a chemical system.

1
Three “Pillars” of Scientific Investigation
⮚ Experiment
⮚ Theory (analytical equations)
⮚ Computational Simulation
⮚ (“theoretical experiments”)

2
⮚Simulation is becoming a third pillar of science, along
with theory and experiment.

⮚Using theory, we develop models: simplified

representations of physical systems.

⮚We test the accuracy of these models in experiment,

and use simulation to help refine this feedback loop.

⮚Anything that can be measured can be simulated,

including properties related to energetics, structures,
and spectra of chemical systems.
3
 The Nobel Prize in Chemistry 1998

John A. Pople Walter

Kohn
The Nobel Prize in Chemistry 1998 was divided equally
between Walter Kohn "for his development of the density-
functional theory" and John A. Pople "for his development of
computational methods in quantum chemistry".
4
 2013 Nobel Prize In Chemistry

"for the development of multiscale models for complex chemical systems”

• Martin Karplus, Université de Strasbourg, France, and Harvard University,
Cambridge, MA, USA

• Michael Levitt, Stanford University, Los Angeles, CA, USA

• Arieh Warshel, University of Southern California (USC), CA, USA 5

Using computational chemistry software you can in particular perform:

o Electronic structure predictions

o Geometry optimizations or energy minimizations
o Conformational analysis and potential energy surfaces (PES)
o Frequency calculations
o Finding transition structures and reaction paths
o Molecular docking: Protein – Protein and Protein-Ligand interactions
o Electron and charge distributions calculations
o Calculations of rate constants for chemical reactions: Chemical
kinetics
o Thermochemistry - heat of reactions, energy of activation, etc.
o Calculation of many other molecular and physical and chemical
properties
o Orbital energy levels and electron density
o Electronic excitation energy 6
• Structure of a molecule in general is how atoms are arranged
in the molecule in the three dimensional space.

• Potential energy surface (PES) is a plot of energy with respect

to various internal coordinates of a molecule such as bond
length, bond angle etc.

7
• The PES is the energy of a molecule as a function of the positions
(coordinates).

• This energy of a system of two atoms depends on the distance

between them.

• At large distances the energy is zero, meaning “no interaction”.

• The attractive and repulsive effects are balanced at the minimum

point in the curve
Potential energy for nuclear motion in a diatomic molecule

9
Potential Energy Surfaces and Mechanism

10
 Conformational Analysis

⮚ Identification of all possible minimum energy structures

(conformations) of a molecule is called conformational analysis.

⮚ Conformational analysis is an important step in computational

chemistry studies as it is necessary to reduce time spent in the
screening of compounds for properties and activities.

11
⮚ The identified conformation could be the local minimum,
global minimum, or any transition state between the
minima.

⮚ Out of the several local minima on the potential energy

surface of a molecule, the lowest energy conformation is
known as the global minimum.
Global minimum

Local minima

12
Local minimum Local minimum

Global minimum

13
Ethane Conformations

14
15
16
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